Esquemas de memorizao e resumos

1 Conceitos bsicos
Element H C N O # of covalent bonds 1 4 3 (or 4) 2 Element F Cl Br I # of covalent bonds 1 1 1 1

Carga formal:

Z = valncia, S = compartilhados, U = no-compartilhados

Ressonncia

Conceitos quntico-mecnicos

Hibridizao sp3

Hibridizao sp2

Hibridizao sp

Resumo de Hibridizao

Teoria VSEPR (RPECV)

2 Grupos funcionais
Hidrocarbonetos

Ligaes polares

Mais grupos funcionais

Resumo de funes orgnicas

Propriedades Fsicas

IV e qumica orgnica

3 Reaes Orgnicas e Mecanismos (introduo)

1 Conceitos bsicos

2 Homlise e Heterlise

3 Reaes cido-Base

4 Carboctions e carbnions, eletrfilos e nuclefilos

5 Setas curvas em reaes orgnicas

6 Fora de cidos e Bases de Bronsted-Lowry (pKa)

7 Prevendo resultado de reaes cido-base

8 Estrutura e Acidez

9 Mudanas de energia nas reaes e mais explicaes para acidez/basicidade

10 O efeito do solvente na acidez

11 Compostos Orgnicos como bases

12 Mecanismo Reacional Sn1

13 cidos e bases em solues no-aquosas

4 Alcanos e cicloalcanos
1 Conceitos Bsicos

2 Forma dos Alcanos

3 Nomenclatura IUPAC

4 Propriedades Fsicas

5 Conformaes

6 Estabilidade dos cicloalcanos, conformaes e isomeria

7 Sntese de Alcanos e Cicloalcanos

8 Informaes baseadas em frmulas moleculares e ndices de deficincia de H

5 Estereoqumica e molculas quirais

1 Quiralidade e Estereoqumica

2 Isomerismo

3 Nomenclatura de estereoismeros

4 Propriedades dos enantimeros

5 Sntese de Molculas Quirais

6 Molculas com mais de um estereocentro

7 Estereoisomerismo de compostos cclicos

8 Reaes e configuraes

9 Separao de enantimeros / Resoluo

10 Compostos com outros tipos de quiralidades

6 Substituies Nucleoflicas e Eliminaes (Haletos)

1 Haletos Orgnicos

2 Reaes de Substituio Nucleoflica (SN2)

3 Reaes de Substituio Nucleoflica (SN1)

4 Fatores afetando SN1 e SN2

5 Sntese orgnica: introduo

6 Reaes de Eliminao

7 Substituies e Eliminaes

8 Resumo

7 Alcenos, Alcinos e mais conceitos dos hidrocarbonetos

1 - Introduo

2 - Nomenclatura

3 Estabilidade Relativa

4 Cicloalcanos

5 Sntese Reaes de Eliminao

6 Alcinos

7 Reaes Caractersticas

8 Sntese Orgnica: conceitos bsicos

9 Reaes de Adio de Alcenos e outras reaes

10 Sntese: mais conceitos

8 RMN e Espectrometria de Massas

1 Ressonncia Magntica Nuclear (RMN) de prtons (RMN-H)

2 Ressonncia Magntica Nuclear (RMN) de Carbono-13

3 Tcnicas de RMN bidimensionais

4 Espectrometria de Massas

9 Reaes Radicalares
1 Conceitos Principais

2 A reao de alcanos com halognios

3 Mais conceitos

10 Alcois e teres
1 Informaes bsicas e gerais

2 Reaes caractersticas

3 Sntese de teres

4 Reaes de teres

5 Resumo das reaes

6 Alcois e compostos carbonlicos

11 Sistemas Conjugados Insaturados

1 Introduo e conceitos bsicos

2 Espectroscopia no Ultravioleta/Visvel (UV-Vis)

3 Reaes em Sistemas Conjugados

12 Sistemas Aromticos
1 Introduo e conceitos bsicos

2 Caractersticas do benzeno

3 Sistemas aromticos conceitos mais gerais

4 Espectroscopia de compostos aromticos

4 Reaes de compostos aromticos

13 Aldedos e Cetonas
1 Introduo e conceitos bsicos

2 Snteses e reaes

3 Identificao de cetonas e aldedos

14 cidos Carboxlicos e Derivados

1 Introduo e conceitos bsicos

2 Reaes no carbono carbonlico

3 Reaes de condensao e de adio conjugada em compostos carbonlicos

15 Aminas
1 Conceitos bsicos

2 Reaes

3 Anlise de Aminas

4 Mais reaes

16 Mais reaes aromticas

Reaes dos compostos orgnicos

1 Algumas reaes importantes, por classes de compostos
Alcanos
Aquecimento Craqueamento X 2 (Cl, Br ou F) Aquecimento ou hv Halogenao
X

etc.

Aquecimento CO2 + H2O Combusto

Alcenos
Br H HO Br O H

Br2 Halogenao

KMnO4 dil. Oxidao Branda

HO

H OH

H R 2N
H HO Br H

NR2

m CPBA Epoxidao
Br H

OsO4 Oxidao Branda

OR HO

H OH

RO -

HBr Adio Markovinkov

1 - O3 2 - H2O
H

Ozonlise
H HO H

1 - Hg(OAc)2, H 2O 2 - NABH4 Oximercuriao Desmercuriao Br2 , ROH

H

Br

Formao de Halolcool
OH

H 2, Pd/C
H

H H

Reduao Cataltica BH3 , THF

B(CHCH3 CHCH3 CH 3) 3 Hidroborao 1 - B2 H6 , 2 - H2 O2 Hidratao Anti-Markovnikov H 2SO4 , H2O

HO H H OH

Hidratao Markovnikov

Alcinos
RLi, THF, -78C R= H Adio de organometlico RMgX, THF Formao de Grignard NaNH2 , -78 C
R R - Na+ MgX Li

Formao de Acetileto H2 , Pd/C Reduo HX Adio Eletroflica

X X R R

BH3 Hidroborao
R
3

Alcois
HBr SN 1 Somente eficiente para tercirio
R1 R3 Br R2

H Nu, Ph3P, DEAD

R3 OH R1 R2

R3 Nu R2

SN 2 Reao de Mitsonobu H2Cr2 O7 Oxidao

R1

R1

R2 O

PCC Oxidao
R1

R2 R3 R3 O R1

H2SO4 Desidratao
R1

+
R2 R1 R2 R3 R2

Aldedos
1 - NaCN, H2 SO 4 2 - H2 O Adio Nucleof lica NaBH4 Reduo com boroidreto 1 - RLi, THF 2 - H2 O Adio de Organometlicos 1 - RMgBr, Et2 O 2 - H2 O
R OH OH R OH OH CN H

Adio de Grignard
O

OH OR

ROH, c. ou base
H

Equlibrio de Hemiacetal
OH

NaHSO3, banho de gelo Adio de bissulfito RNH2 , H cat. Formao de imina

+

SO3 -Na+

R N

NH3 , H2, Ni, Presso Reduo Aminativa

NH 2

NH2

NaCN, NH4 Cl Sntese de Aminocido de Strecker c. ou Base Enolizao

OH

CN H

H2O, H

NH 2 CO2 H H

Cetonas
1 - NaCN, H2 SO 4 2 - H2 O Adio Nucleof lica
OH OH CN O

Br2 , HOAc
Br

Halogenao Via Enolato

OMe

NaBH4 Reduo com boroidreto 1 - RLi, THF 2 - H2 O Adio de Organometlicos 1 - RMgBr, Et2 O 2 - H2 O Adio de Grignard
O OH R OH R

t-BuOK Formao de Enol ter

OH OR

ROH, c. ou base Equlibrio de Hemiacetal

OH

NaHSO3, banho de gelo Adio de bissulfito RNH2 , H+ cat. Formao de imina

H N R1 R2 R N

SO3 -Na+

, H + cat.

R1 N

R2

Formao de enamina NH3 , NaCNBH3 Reduo Aminativa Sal de Fosfnio, NaH Reao de Wittig
NH2

cidos Carboxlicos
O

SOCl2 / PCl5 / (COCl)2 Substituio Nucleof lica ROH, H

+

Cl O

Substituio Nucleof lica

O O

NH3 Reao cido-Base HCl Reao cido-Base BH3 , THF Reduo

OH OH O- NH4 + +OH Cl-

OH

Anidridos
O

H2 O Substituio Nucleof lica

O O O OH

ROH Substituio Nucleof lica

O OR

NH3 Substituio Nucleof lica

NH2

steres
O

H2O, c. ou base Substituio Nucleof lica

OH OH

RMgX Substituio Nucleof lica NH3

OR O

R R

Subst. Nucl. e Reduo LiAlH4 ou LiBH4 Reduo

O

NH2

OH

DIBAL, Hex, - 70 C Reduo

H

Cloretos de cido
O

H2 O Substituio Nucleof lica

O OH

ROH Substituio Nucleof lica

O OR

NH3
O

Substituio Nucleof lica

Cl O

NH2 O

RCO2 Substituio Nucleof lica

O O R

R 2CuLi Substit. Nucl. com Cupratos

H N O O N R OMe

Formao de Amida de Weinreb

teres
HBr ou HCl conc.
X

Clivagem
O

H2 SO4 Eliminao O2 Autoxidao

O O

Amidas
O

H2 O, c. ou bas. fort
O

Reduo
NH2

OH

LiALH4 Reduo
NH2

Compostos Carbonlicos a,b-Insaturados

CN O

KCN, HCN Produto Termodinmico

OH R

KCN, HCN Produto Cintico R2 NH+ Adio Conjugad a ROH, c. ou base Adio Conjugad a
O SR O O R O NR O

CN R

RSH
R

Adio Conjugad a
X O

HX Adio Conjugad a NaBH4, R = H Reduo NaBH4 Reduo RMgX, CuCl Adio Conjugad a com CuCl NaBH4 , CeCl3 Reduo

OH

OH

R R O

R OH

Aminas
NH2

CH2 =O , NaCNBH3
R2

R1

Formao de Amida Terciria

R1

R2

Nitrilas
1 - DIBAL, -70 C
CN O

2 - H2 O, H

Haletos de Alquila
Mg, THF Formao de Grignard Li, EtOH
X MgX

Formao de organoltio EtOH, base fraca Substituio EtOH, Base f orte Eliminao

Li

OEt

Nitrocompostos
H2 , Pt ou Pd
NO2

Reduo

N H

Compostos de Grignard
O HO R2 R1 R1 R2

Adio de Grignard
R MgX

MgX

Adio de Grignard 1 - Co2 , Et2O + 2- H Formao de c. Carb. do CO2

OH

Organoltios
O HO R2 R1 R1 R2

Adio de organometlico
R

Li OR

Adio de Organometlico
OR

Ortolitiao RX
R Li

Li

Troca Halognio - Ltio MgBr 2 , THF Transmetalao

MgBr

CeCl, THF Transmetalao

CeCl2

Benzeno
Br

Br2 , AlCl3 Bromao

NO2

HNO3 , H 2SO4 Nitrao

SO2 OH

H2SO4 + SO3 Sulfonao

R

RX + AlCl3 Alqulao de Friedel-Craf ts

O

RCOCl + AlCl3 Acilao de Friedel-Craf ts

H2, Ni, 50C, 100 atm Reduo Cataltica

OH OH

RLi
Li

Ortolitiao

2 Informaes importantes sobre classes de reaes

1 SN1, SN2, E1, E2 e E1cb

2 Substituio Eletroflica Aromtica

3 Reaes na carbonila
Adio Nucleoflica

Trajetria de Burgi-Dunitz

Reaes com organometlicos

Adio Conjugada

Substituio Nucleoflica

Substituio Nucleoflica com perda do oxignio

Reaes Eletroflicas

4 Reaes cido-Base

5 Reaes de Oxidao e Reduo

6 Grupos Protetores

3 Reaes orgnicas nomeadas

Acetoacetic Ester Synthesis

Acyloin Condensation

Alder-Ene Reaction (Ene Reaction)

Aldol Addition (Aldol Reaction)

Mechanism of the Aldol Addition

Aldol Condensation

Azo Coupling

Baeyer-Villiger Oxidation

Balz-Schiemann Reaction

Beckmann Rearrangement

Bergman Cyclization (Bergman Cycloaromatization)

Birch Reduction

Blaise Reaction

Brook Rearrangement

Brown Hydroboration

Cannizzaro Reaction

Corey-Bakshi-Shibata Reduction (Itsuno-Corey Reduction)

Claisen Rearrangement

Claisen Condensation

Clemmensen Reduction

Corey-Fuchs Reaction

Corey-Kim Oxidation

Corey-Seebach Reaction (Seebach Umpolung)

Cross Metathesis

Curtius Rearrangement

Dakin Reaction

Delpine Reaction

Dess-Martin Oxidation

Diazotisation

Dieckmann Condensation

Diels-Alder Reaction

Directed ortho Metalation (DOM)

Epoxidation (Prilezhaev Reaction)

Fischer Esterification (Fischer-Speier Esterification)

Favorskii Reaction

Fischer Indole Synthesis

Friedel-Crafts Acylation

Friedel-Crafts Alkylation

Friedlaender Synthesis

Fries Rearrangement

Fukuyama Coupling

Fukuyama Reduction

Gabriel Synthesis

Grignard Reaction (Grignard Reagents)

Grubbs Reaction (Olefin Metathesis)

Haloform Reaction

Heck Reaction

Hell-Volhard-Zelinsky Reaction

Henry Reaction

Hofmann Elimination

Hofmann's Rule

Horner-Wadsworth-Emmons Reaction (Wittig-Horner Reaction)

Ireland-Claisen Rearrangement

Iwanow Reaction (Ivanov Reaction)

Jacobsen Epoxidation (Jacobsen-Katsuki Epoxidation)

Jones Oxidation

Kochi Reaction

Kolbe Electrolysis

Kolbe Nitrile Synthesis

Kolbe-Schmitt Reaction

Kumada Coupling

Lawesson's Reagent

Leuckart Thiophenol Reaction

Luche Reduction

Mannich Reaction

Markovnikov's Rule

Anti-Markovnikov

McMurry Reaction

Michael Addition

Mitsunobu Reaction

Mukaiyama Aldol Addition

Nazarov Cyclization (Nazarov Reaction)

Negishi Coupling

Nozaki-Hiyama Coupling (Nozaki-Hiyama-Kishi Reaction)

Nucleophilic Substitution (SN1 SN2)

Nucleophilic substitution is the reaction of an electron pair donor (the nucleophile, Nu) with an electron pair acceptor (the electrophile). An sp3-hybridized electrophile must have a leaving group (X) in order for the reaction to take place.

Mechanism of Nucleophilic Substitution The term SN2 means that two molecules are involved in the actual transition state:

The departure of the leaving group occurs simultaneously with the backside attack by the nucleophile. The SN2 reaction thus leads to a predictable configuration of the stereocenter - it proceeds with inversion (reversal of the configuration). In the SN1 reaction, a planar carbenium ion is formed first, which then reacts further with the nucleophile. Since the nucleophile is free to attack from either side, this reaction is associated with racemization.

In both reactions, the nucleophile competes with the leaving group. Because of this, one must realize what properties a leaving group should have, and what constitutes a good nucleophile. For this reason, it is worthwhile to know which factors will determine whether a reaction follows an SN1 or SN2 pathway. Very good leaving groups, such as triflate, tosylate and mesylate, stabilize an incipient negative charge. The delocalization of this charge is reflected in the fact that these ions are not considered to be nucleophilic.

Hydroxide and alkoxide ions are not good leaving groups; however, they can be activated by means of Lewis or Brnsted acids.

Epoxides are an exception, since they relieve their ring strain when they undergo nucleophilic substitution, with activation by acid being optional:

Triflate, tosylate and mesylate are the anions of strong acids. The weak conjugate bases are poor nucleophiles. Nucleophilicity increases in parallel with the base strength. Thus, amines, alcohols and alkoxides are very good nucleophiles. Base strength is a rough measure of how reactive the nonbonding electron pair is; thus, it is not necessary for a nucleophile to be anionic. Under substitution conditions, amines proceed all the way to form quaternary salts, which makes it difficult to control the extent of the reaction.

However, as a nucleophile's base strength and steric hindrance increase, its basicity tends to be accentuated. If there are abstractable protons at the -position of the electrophile, an elimination pathway can compete with the nucleophilic substitution.

An additional factor that plays a role is the character of the solvent. Increasing stabilization of the nucleophile by the solvent results in decreasing reactivity. Thus, polar protic solvents will stabilize the chloride and bromide ions through the formation of hydrogen bonds to these smaller anions. Iodide is a comparatively better nucleophile in these solvents. The reverse behavior predominates in aprotic polar media. The solvent also plays an important role in determining which pathway the reaction will take, SN1 versus SN2. It may safely be assumed that a primary-substituted leaving group will follow an SN2 pathway in any case, since the formation of the corresponding unstable primary carbenium ion is disfavored. Reaction by the S N1 pathway is highly probable for compounds with tertiary substitution, since the corresponding tertiary carbenium ion is stabilized through hyperconjugation:

The better the solvent stabilizes the ions, the more probable that the reaction will follow an SN1 pathway (e.g., in polar protic solvents such as water/acetone). The more highly substituted is the incipient carbenium ion, the more probable that the reaction will follow an SN1 pathway. The more unreactive the nucleophile, the more probable it becomes that a reaction with secondary and tertiary electrophiles will follow an SN1 pathway. A weaker nucleophile is not as effective in the backside attack, since this location is sterically shielded, especially in the case of tertiary substrates. Carbenium ions are planar and therefore less sterically hindered, and are naturally more reactive as electrophiles than the uncharged parent compound. The hydrolysis of tert-butyl chloride is a typical SN1 reaction:

Oppenauer Oxidation

Ozonolysis (Criegee Mechanism)

Paal-Knorr Furan Synthesis

Paal-Knorr Pyrrole Synthesis

Passerini Reaction

Peterson Olefination

Reformatsky Reaction

Ring Closing Metathesis (RCM)

Ring Opening Metathesis (Polymerization) - ROM(P)

Ritter Reaction

Robinson Annulation

Saytzeff's Rule

Saytzeff Rule implies that base-induced eliminations (E2) will lead predominantly to the olefin in which the double bond is more highly substituted, i.e. that the product distribution will be controlled by thermodynamics.

The use of sterically hindered bases raises the activation energy barrier for the pathway to the product predicted by Saytzeff's Rule. Thus, a sterically hindered base will preferentially react with the least hindered protons, and the product distribution will be controlled by kinetics. Shapiro Reaction

Sharpless Aminohydroxylation (Sharpless Oxyamination)

Sharpless Dihydroxylation

Sharpless Epoxidation

Stille Coupling

Strecker Synthesis

Suzuki Coupling

Swern Oxidation

Van Leusen Reaction

Wacker-Tsuji Oxidation

Weinreb Ketone Synthesis

Williamson Synthesis

Wittig Reaction

Wolff-Kishner Reduction

Woodward Reaction (Woodward cis-Hydroxylation)

Wurtz Reaction

Wurtz-Fittig Reaction

Yamaguchi Esterification